O{3 beta alkane phosphates

ABSTRACT

WHEREIN R can be selected from the group consisting of hydrogen, alkyl and aryl; R1 is alkyl; R2 can be selected from hydrogen, alkyl, alkylcyano, thioalkyl, alkynyl, benzothiazolo, imidazolo, aryl and substituted aryl with the substituents being selected from nitro, alkyl, halogen, cyano, thioalkyl, haloalkyl and amido; X can be oxygen, sulfur or amino, provided that when X is oxygen or sulfur R2 is other than hydrogen. Compounds of the present invention are active insecticides and miticides.   New compounds having the generic formula:

iinited States Patent Gutman Jan. 28, 1975 O'BETA ALKANE PHOSPHATES [75] Inventor: Arnold D. Gutman, Berkeley, Calif.

[73] Assignee: Stauffer Chemical Company, New

York, NY.

[22] Filed: Oct. 19, 1972 [21] Appl. No.: 298,979

Related U.S. Application Data [62] Division of Ser, No. l23,467, March 11. 197i abandoned.

[52] U.S. Cl. 260/956, 260/304, 260/306, 260/309, 260/940, 260/943, 260/948, 260/949, 260/954, 260/955, 424/200, 424/202, 424/210, 424/211, 424/216, 424/218, 424/222 [5 1] Int. Cl. C07f 9/38, A0ln 9/36 [58] Field of Search 260/956 [56] References Cited UNITED STATES PATENTS 3,058,878 10/1962 Newallis et al. 260/956 X Primary Examiner-Anton H. Sutto Attorney, Agent, or Firm-Daniel C. Block [57] ABSTRACT New compounds having the generic formula:

wherein R can be selected from the group consisting of hydrogen, alkyl and aryl; R is alkyl; R can be selected from hydrogen, alkyl, alkylcyano, thioalkyl, alkynyl, benzothiazolo, imidazolo, aryl and substituted aryl with the substituents being selected from nitro, alkyl, halogen, cyano, thioalkyl, haloalkyl and amido; X can be oxygen, sulfur or amino, provided that when X is oxygen or sulfur R is other than hydrogen. Compounds of the present invention are active insecticides and miticides.

26 Claims, N0 Drawings 1 OBETA ALKANE PHOSPHATES DESCRIPTION OF THE INVENTION P -"Um wherein R can be selected from the group consisting of hydrogen, alkyl and aryl; R is alkyl; R can be selected from hydrogen, alkyl, alkylcyano, thioalkyl, alkynyl, bcnzothiazolo, imidazolo, aryl and substituted aryl with the substituents being selected from nitro, alkyl, halogen, cyano, thioalkyl, haloalkyl and amido; X can be oxygen, sulfur or amino. provided that when X is oxygen or sulfur R is other than hydrogen.

In general, the above-noted compounds can be prepared by reacting an appropriate alcohol with ethylthionophosphine sulfide to form a reactive mercaptan. The mercaptan is then treated with a halide compound in the presence ofa base such as triethylamine to form the end product. In the alternative, an appropriate alcohol can be reacted with a dihalothiophosphonous derivative to obtain a reactive thiochloridate phosphonous intermediate which is reacted with an appropriate compound to form the end product.

In order to illustrate the merits of the present invention, the following examples are provided:

EXAMPLE 1 O-crotyl-S-propargyl, ethylphosphonodithioate 12.4 grams (0.05 mole) of ethylthionophosphine sulfide is combined with 200 ml. of dioxane in a 600 ml. beaker. The mixture is stirred at room temperature and 7.2 grams (0.1 mole) of crotyl alcohol is added and the resulting mixture is stirred until a clear solution is obtained. The solution is cooled in an ice bath to C. and 11.9 grams (0.1 mole) of propargyl bromide is added followed by the addition of 10.1 grams (0.1 mole) of triethylamine over a period of 10 minutes. The resulting mixture is stirred at room temperature for Compound No x 1 hour, then poured into 300 mls. of benzene. The benzene mixture is washed with 200 ml. of water, ml. of saturated sodium bicarbonate solution followed by two 100 ml. portions of water. The benzene phase is dried over anhydrous magnesium sulfate and evaporated under reduced pressure to yield 17.2 grams of product. n 1.5375.

EXAMPLE 2 O-allyl-O-ethylphosphorothiochloridate 54 g. (0.5 mole) of allyl alcohol, 56 g. (0.5 mole) of potassium t-butoxide and 500 ml. oftetrahydrofuran is combined and heated under reflux for one hour. The resulting solution is cooled to room temperature and is added over a period of one hour to a stirring solution of 89.5 g. (0.5 mole) of ethyldichlorothiophosphonate. The reaction temperature during the addition is maintained at -10 to -5. After the addition is complete, the mixture is allowed to warm to room temperature and is stirred for one hour. The mixture is then poured into 500 ml. of benzene and washed with three 300 ml. portions of water. The benzene phase is dried with anhydrous MgSO and evaporated under reduced pressure to yield 101 g. of the desired product. 11,, 1.5347.

EXAMPLE 3 O-allyl-O-(3-methy1-4-nitrophenyl)-ethylphosphonothioate 9.2 grams (0.06 mole) of 3-methyl-4-nitrophenol is combined with 2.4 grams (0.06 mole) of caustic and 20 ml. of water in a 500 ml. three-necked flask fitted with a stirrer, thermometer, and dropping funnel. The mixture is stirred and 11.1 grams (0.06 mole) of the compound of Example 2 in 200 ml. of tetrahydrofuran is added over a period of 30 minutes. The resulting mixture is stirred and heated under reflux for 2 hours, cooled and poured into 400 ml. of benzene. The benzene mixture is washed with 200 ml. of water, 200 ml. of dilute caustic solution, followed by two 200 ml. portions of water. The benzene phase is dried with anhydrous MgSO and evaporated under reduced pressure to yield 7.7 grams of product. n 1.5380.

Other compounds were prepared in an analogous manner starting with the appropriate materials as outlined above. The following is a table of compounds representative of those embodied by the present invention. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

TABLE I Ft R-CH=CH-CI I -O-$-X-R 5 1 32 CH C H CH -C CH CH C 11 CH -SC H CH C 11 CI-I -C N H C 11 CH -C"="CH Compound N0.

TABLE I gCont.

SCH

I I I [jgjgj O 2 2 N N TABLE I Cont.

Compound 5.1

53 0 CH CH 54 0 H CH 55 0 CH CH 56 0 CH CH 57 0 CH CH 58 0 CH CH 59 O H CH Entomological Testing Methods 1. House Fly [Musca domestica (L.)]

A stock solution containing 100 ug/ml ofthe toxicant in an appropriate solvent is'prepared. Aliquots of this solution are combined with one ml. of an acetonepeanut oil solution in a dish, 55 mm in diameter, and allowed to dry. The aliquots are varied to achieve desired toxicant concentrations ranging from 100 pg per dish to that at which 50% mortality is obtained. The dishes are placed in a circular cardboard-cage, closed on the bottom with cellophane and covered on top with cloth netting. Twenty-five female house flies are introduced into the cage and the percentmortality is recorded after 48 hours. LD-50 values are expressed in terms of pg per female flies.

ll. German Cockroach [Blattella germanica (Linne')] Ten one-month old nymphs are placed into a circular cardboard cage sealed on one end with cellophane and covered by cloth netting on the other Aliquots of the toxicant, dissolved in an appropriate solvent, are diluted in water to which has been added 0.0002% of a conventional wetting agent such aspolyoxyethylene sorbitan monolaurate ether of alkylated phenols blended with organic sullonates. Test concentrations range from 0.1% to that at which 50% mortality is obtained. Each of these aqueous suspensions are sprayed onto theinsects, through the cloth netting, by means of a hand spray gun. Percent mortality is recorded after 72 hours and the LD-SOvalues are expressed as percent of toxicant in the aqueous spray. lll. Lygus Bug [Lygus hesperus (Knight)] Same as for the German cockroach (ll) except that the test concentrations range from 0.05% to that at which 50% mortality is obtained.

IV. Salt-marsh Caterpillar [Estigmene ucrea (Drury)] Test solutions are prepared in an identical manner and concentrations are the same as those for the German cockroach (ll). Sections of bitter dock (Rumex obtuszfolius) leaves, 1-1.5 inches in length are immersed'in the test solutions for l0-l5 seconds and placed on a wire screen to dry. The dried leaf is placed on a moistened piece of filter paper in a petri dish and infested with five third-instar larvae. Mortality of the larvae is recorded after 72 hours and the LD-SO values are expressed as percent active ingredient in the aqueous suspensions.

V. Beet Armyworm [Spodoptera exigua (H'u'bner)] Same as salt-marsh caterpillar (IV) except that leaves of Romaine lettuce (Latuca sativa) are used as the host plant.

Vl. Tobacco Budworm [Heliothis virescens (F.)]

Same as for Beet armyworm (V).

Vll. BlackBean Aphid [Aphis fabae (Scop.)]

Nasturtium (Tropaeolum sp.) plants, approximately 23 inches tall, are transplanted into sandy loam soil in 3-inch clay pots and infested with 50-75 aphids of mixed ages. Twenty-four hours later they are sprayed,

wherein R is selected from the group consisting of hydrogen and alkyl; R, is alkyl; R is selected from phenyl and substituted phenyl with the substituents being selected from alkyl and halogen; X is oxygen or sulfur.

2. A compound as set forth in claim 1 wherein X is S, R is CH,, R, is C H and R is 3. A compound as set forth in claim 1 wherein X is O, R is CH R, is C H and R, is

4. A compound as set forth in claim 1 wherein X is O, R is CH R, is C H and R is 5. A compound as set forth in claim 1 wherein X is S, R is H, R, is C H and R is 6. A compound as set forth in claim 1 wherein X is S, R is H, R1 iS C2H5 and R2 iS 7. A compound as set forth in claim 1 where in X is S, R is CH R, is C H and R is 8. A compound as set forth in claim 1 wherein X is S, R is C i'ig; R] is C2H5 and R2 iS 9. A compound as set forth in claim 1 wherein X is O, R is CH,, R, is C l-l and R is 10. A compound as set forth in claim 1 wherein X is O, R is H, R, is C H and R is 11. A compound as set forth in claim 1 wherein X is S, R is H, R, is C H and R is 12. A compound'as set forth in claim I wherein X is O, R is CH R, is C H is 13. A compound as set forth in claim 1 wherein X is S, R is H, R, is C H and R is 14. A compound as set forth in claim 1 wherein X is O, R is H, R, is C H and R is 15. A compound as set forth in claim 1 wherein X is O, R iS H, R1 is C2H5 and R2 iS 16. A compound as set forth in claim 1 wherein X is S, R iS H, R] is CH3 and R2 is 17. A compound as set forth in claim 1 wherein X is S, R is H, R, is CH, and R, is

18. A compound as set forth in claim 1 wherein X is S, R is CH,, R, is CH, and R, is

19. A compound as set forth in claim 1 wherein X is S, R is CH3, R1 iS CH3 and R2 i8 15 16 20. A compound as set forth in claim 1 wherein X is 24. A compound as set forth in claim 1 wherein X is S, R is CH3, R1 iS CH3 R2 iS O, R iS CH3, R1 is CH3 and R2 is Cl Br. Q 5 c1. 21. A compound as set forth in claim 1 wherein X is Cl S, R iS CH3, R1 iS CH3 and R2 is 25. A compound as set forth in claim 1 wherein X is @03 0, R is CH R is CH and R is C1 22. A compound as set forth in claim 1 wherein X is S, R is H, R] is CH3 and R2 iS 26. A compound as set forth in claim 1 wherein X is O, R is H, R] iS CH3 and R2 iS 23. A compound as set forth in claim 1 wherein X is 1 S, R is H, R, is CH and R is v Cl 

2. A compound as set forth in claim 1 wherein X is S, R is CH3, R1 is C2H5 and R2 is
 3. A compound as set forth in claim 1 wherein X is O, R is CH3, R1 is C2H5 and R2 is
 4. A compound as set forth in claim 1 wherein X is O, R is CH3, R1 is C2H5 and R2 is
 5. A compound as set forth in claim 1 wherein X is S, R is H, R1 is C2H5 and R2 is
 6. A compound as set forth in claim 1 wherein X is S, R is H, R1 is C2H5 and R2 is
 7. A compound as set forth in claim 1 where in X is S, R is CH3, R1 is C2H5 and R2 is
 8. A compound as set forth in claim 1 wherein X is S, R is CH3, R1 is C2H5 and R2 is
 9. A compound as set forth in claim 1 wherein X is O, R is CH3, R1 is C2H5 and R2 is
 10. A compound as set forth in claim 1 wherein X is O, R is H, R1 is C2H5 and R2 is
 11. A compound as set forth in claim 1 wherein X is S, R is H, R1 is C2H5 and R2 is
 12. A compound as set forth in claim 1 wherein X is O, R is CH3, R1 is C2H5 is
 13. A compound as set forth in claim 1 wherein X is S, R is H, R1 is C2H5 and R2 is
 14. A compound as set forth in claim 1 wherein X is O, R is H, R1 is C2H5 and R2 is
 15. A compound as set forth in claim 1 wherein X is O, R is H, R1 is C2H5 and R2 is
 16. A compound as set forth in claim 1 wherein X is S, R is H, R1 is CH3 and R2 is
 17. A compound as set forth in claim 1 wherein X is S, R is H, R1 is CH3 and R2 is
 18. A compound as set forth in claim 1 wherein X is S, R is CH3, R1 is CH3 and R2 is
 19. A compound as set forth in claim 1 wherein X is S, R is CH3, R1 is CH3 and R2 is
 20. A compound as set forth in claim 1 wherein X is S, R is CH3, R1 is CH3 and R2 is
 21. A compound as set forth in claim 1 wherein X is S, R is CH3, R1 is CH3 and R2 is
 22. A compound as set forth in claim 1 wherein X is S, R is H, R1 is CH3 and R2 is
 23. A compound as set forth in claim 1 wherein X is S, R is H, R1 is CH3 and R2 is
 24. A compound as set forth in claim 1 wherein X is O, R is CH3, R1 is CH3 and R2 is
 25. A compound as set forth in claim 1 wherein X is O, R is CH3, R1 is CH3 and R2 is
 26. A compound as set forth in claim 1 wherein X is O, R is H, R1 is CH3 and R2 is 